WO2021075265A1 - 電磁波シールド用ペースト - Google Patents

電磁波シールド用ペースト Download PDF

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Publication number
WO2021075265A1
WO2021075265A1 PCT/JP2020/037270 JP2020037270W WO2021075265A1 WO 2021075265 A1 WO2021075265 A1 WO 2021075265A1 JP 2020037270 W JP2020037270 W JP 2020037270W WO 2021075265 A1 WO2021075265 A1 WO 2021075265A1
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Prior art keywords
mass
electromagnetic wave
wave shielding
less
resin
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PCT/JP2020/037270
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English (en)
French (fr)
Japanese (ja)
Inventor
大佑 橋本
ジョランダ イルマ カポグリス
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ナミックス株式会社
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Priority to JP2021552304A priority Critical patent/JPWO2021075265A1/ja
Publication of WO2021075265A1 publication Critical patent/WO2021075265A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to an electromagnetic wave shielding paste that forms electromagnetic interference (EMI) in an electronic package.
  • EMI electromagnetic interference
  • electronic devices such as power amplifiers, Wi-Fi / Bluetooth modules, and flash memories are mounted on boards built into electronic devices such as mobile phones, smartphones, notebook computers, and tablet terminals.
  • electronic components may malfunction due to electromagnetic waves from the outside. On the contrary, the electronic component becomes a source of electromagnetic noise, which may cause malfunction of other electronic components.
  • SoC system-on-chip
  • SiP system-in-package
  • MCM multi-chip module
  • Reference 1 discloses a conductive formulation containing a resin and a curing agent that fills the gaps or grooves formed in the substrate on which the electronic components are mounted in order to protect the electronic components from electromagnetic interference (EMI). ing.
  • EMI electromagnetic interference
  • EMI electromagnetic interference
  • the gaps or grooves for protecting the parts mounted on the board from electromagnetic interference (EMI) and the like tend to become narrower.
  • EMI electromagnetic interference
  • voids are formed in the conductive composition filled in the gaps or grooves due to the narrowing of the gaps or grooves formed in the substrate, it becomes more difficult to discharge the voids.
  • One aspect of the present invention is to provide an electromagnetic wave shielding paste that can be easily filled in the gap or groove formed in the substrate and can suppress the occurrence of voids and sink marks of the resin after filling.
  • the means for solving the above problems are as follows, and the present invention includes the following aspects.
  • the first aspect of the present invention is (A) conductive particles, (B) a resin having a volatility in the range of 0.1% by mass or more and 20% by mass or less after holding at 130 ° C. for 60 minutes.
  • the second aspect of the present invention is an electronic component using the electromagnetic wave shielding paste.
  • an electromagnetic wave shielding paste that can easily fill the gaps or grooves formed in the substrate and suppress the occurrence of voids and sink marks of the resin after filling, and an electronic component using the same. it can.
  • the electromagnetic wave shielding paste according to the present disclosure will be described based on the embodiment.
  • the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following paste for electromagnetic wave shielding.
  • the electromagnetic wave shielding paste according to the first embodiment of the present invention is (A) Conductive particles and (B) A resin having a volatilization rate of 0.1% by mass or more and 20% by mass or less after being held at 130 ° C. for 60 minutes. (C) The viscosity at 25 ° C., which contains peroxide and is measured by a Brookfield viscometer at a rotation speed of 50 rpm, is in the range of 10 mPa ⁇ s or more and 200,000 mPa ⁇ s or less.
  • the electromagnetic wave shielding paste according to the first embodiment of the present invention contains (B) a resin having a volatilization rate of 0.1% by mass or more and 20% by mass or less after being held at 130 ° C. for 60 minutes.
  • the volatilization rate of the resin contained in the electromagnetic wave shielding paste is low, it is possible to suppress the generation of voids due to the volatilization of the components contained in the electromagnetic wave shielding paste, and a sufficient electromagnetic wave shielding effect can be exhibited.
  • the electromagnetic wave shielding paste contains a resin having a low volatilization rate in which the volatilization rate after holding at 130 ° C. for 60 minutes is in the range of 0.1% by mass or more and 20% by mass or less, the resin is cured.
  • the volatility in the present specification refers to the ratio of the mass volatilized to the mass of the resin before holding after holding at 130 ° C. for 60 minutes, and is specifically calculated by the following formula (1).
  • Volatile rate (mass%) (mass before holding-mass after holding) ⁇ mass before holding x 100
  • the viscosity of the electromagnetic wave shielding paste at 25 ° C. measured by a Brookfield type (B type) viscometer at a rotation speed of 50 rpm is within the range of 10 mPa ⁇ s or more and 200,000 mPa ⁇ s or less, a narrow gap or a narrow gap or The groove can be sufficiently filled, and workability is good.
  • the viscosity of the electromagnetic wave shielding paste at 25 ° C. measured by a Brookfield viscometer at a rotation speed of 50 rpm is preferably in the range of 100 mPa ⁇ s or more and 100,000 mPa ⁇ s or less, and more preferably 1,000 mPa ⁇ s or more. It is within the range of 50,000 mPa ⁇ s or less.
  • the viscosity of the electromagnetic wave shielding paste can be measured using, for example, a Brookfield type viscometer (product number: DV-3T, manufactured by Brookfield).
  • Conductive particles preferably contain at least one metal selected from the group consisting of Ag, Cu and Ni, and are conductive particles composed of a single metal of Ag, Cu or Ni. It may be conductive particles which are alloys or composites of at least one metal selected from the group consisting of Ag, Cu and Ni. Further, an organic substance such as a resin or an inorganic substance other than a metal may be used as a core and coated with the above-mentioned metal component.
  • the conductive particles those having a shape such as a spherical shape, an elliptical spherical shape, a needle shape, a flake (scale) shape, or an indefinite shape can be used.
  • the size of the conductive particles (A) can be observed using a scanning electron microscope (SEM) using a scanning electron microscope (SEM), and an average value can be calculated by arbitrarily measuring 50 particles from the SEM image.
  • SEM scanning electron microscope
  • SEM scanning electron microscope
  • an average value can be calculated by arbitrarily measuring 50 particles from the SEM image.
  • the shape of the particles is spherical
  • the average value is used as the average particle size
  • the shape is needle-shaped, elliptical spherical, flake-shaped, or indefinite
  • the average value on the long axis is used as the average particle size. And said.
  • the average particle size is preferably in the range of 0.01 ⁇ m or more and 50 ⁇ m or less, and more preferably in the range of 0.05 ⁇ m or more and 40 ⁇ m or less. More preferably, it is in the range of 0.1 ⁇ m or more and 20 ⁇ m or less.
  • the average particle size (major axis average value) is 0.01 ⁇ m or more and 50 ⁇ m or less, and the aspect ratio is The ratio is preferably in the range of 5 or more and 200 or less, and more preferably in the range of 10 or more and 150 or less.
  • Electromagnetic wave shielding paste when the average particle size of the conductive particles is in the range of 0.01 ⁇ m or more and 50 ⁇ m or less, or when the average particle size (major axis average value) is in the range of 0.01 ⁇ m or more and 50 ⁇ m or less.
  • the conductive particles have good dispersibility, can be sufficiently filled in narrow gaps or grooves, and can exhibit an electromagnetic wave shielding effect.
  • the content of the conductive particles (A) is preferably in the range of 60% by mass or more and 97% by mass or less with respect to 100% by mass of the total amount of the (A) conductive particles and the (B) resin, which is more preferable. Is in the range of 65% by mass or more and 95% by mass or less, more preferably in the range of 70% by mass or more and 92% by mass or less, and particularly preferably in the range of 75% by mass or more and 90% by mass or less.
  • the content of (A) conductive particles is 60% by mass or more and 97% by mass or less with respect to 100% by mass of the total amount of (A) conductive particles and (B) resin blended in the electromagnetic wave shielding paste. If it is within the range, a sufficient electromagnetic wave shielding effect can be exhibited by a cured product that is filled in a narrow gap or groove and cured.
  • the volatilization rate of the resin (B) contained in the electromagnetic wave shielding paste after being held at 130 ° C. for 60 minutes is in the range of 0.1% by mass or more and 20% by mass or less, preferably 0.15% by mass. It is in the range of% or more and 18% by mass or less, and more preferably in the range of 0.2% by mass or more and 15% by mass or less. If the volatilization rate of the resin (B) contained in the electromagnetic wave shielding paste after being held at 130 ° C. for 60 minutes is within the range of 0.1% by mass or more and 20% by mass or less, the volatilization rate of the resin is low and there are gaps or grooves.
  • the components contained in the electromagnetic wave shielding paste are difficult to volatilize, and it is possible to suppress the generation of voids and the sinking of the resin (dents on the surface of the cured product) that are likely to occur due to shrinkage due to volatilization. Can be done.
  • the volatile rate of the resin (B) after being held at 130 ° C. for 60 minutes is within the range of 0.1% by mass or more and 20% by mass or less, and the peroxide (C) described later serves as a thermal radical polymerization initiator and polymerizes. It is preferable that the resin has a functional group that initiates the above, and preferably a (meth) acrylic resin.
  • the resin (B) has a volatilization rate in the range of 0.1% by mass or more and 20% by mass or less after being held at 130 ° C. for 60 minutes, and if it is liquid, the (C) peroxide is thermally radically polymerized. It acts as an initiator and polymerizes.
  • the resin (B) may be a monomer, an oligomer, or a polymer.
  • the (meth) acrylic resin is preferably liquid.
  • (meth) acrylic means acrylic or methacrylic
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate, respectively.
  • the viscosity of the resin (B) at 25 ° C. measured at a rotation speed of 50 rpm is preferably in the range of 1 mPa ⁇ s or more and 5,000 mPa ⁇ s or less, and more preferably 5 mPa ⁇ s or more and 3,500 mPa ⁇ s or less. It is within the range, more preferably within the range of 10 mPa ⁇ s or more and 2,000 mPa ⁇ s or less.
  • the viscosity of the electromagnetic wave shielding paste can be adjusted within a suitable range.
  • the viscosity of the resin (B) and the viscosity of the electromagnetic wave shielding paste can be measured using, for example, a Brookfield type viscometer (product number: DV-3T, manufactured by Brookfield).
  • Examples of the (meth) acrylic resin include esters of polyhydric alcohol compounds and unsaturated carboxylic acids, alkylacrylamide, and the like.
  • esters of the polyhydric alcohol compound and the unsaturated carboxylic acid specific examples include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • methacrylic acid ester examples include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate, trimethylol ethanetrimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol.
  • acrylamide examples include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N, N'-methylbis (meth) acrylamide, and N. , N-dimethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide and the like.
  • the content of the resin (B) is preferably in the range of 3% by mass or more and 40% by mass or less, more preferably 5 with respect to 100% by mass of the total amount of the conductive particles (A) and the resin (B). It is in the range of mass% or more and 35% by mass or less, more preferably in the range of 8% by mass or more and 30% by mass or less, and particularly preferably in the range of 10% by mass or more and 25% by mass or less.
  • the content of (B) resin is within the range of 3% by mass or more and 40% by mass or less with respect to 100% by mass of the total amount of (A) conductive particles and (B) resin mixed in the paste for electromagnetic wave shielding.
  • the electromagnetic wave shielding paste can be filled without forming voids in the narrow gaps or grooves. Further, if the content of (B) resin is within the range of 3% by mass or more and 40% by mass or less, and due to the resin (B) having a low volatile rate, voids and sink marks of the resin (surface of the cured product) are formed even during curing. It is possible to suppress the formation of dents) and form a cured product that exerts a sufficient electromagnetic wave shielding effect.
  • the content of the resin (B) with respect to the total amount of the electromagnetic wave shielding paste is preferably in the range of 3% by mass or more and 40% by mass or less, and more preferably in the range of 4% by mass or more and 34% by mass or less. It is more preferably in the range of 5% by mass or more and 29% by mass or less, and particularly preferably in the range of 6% by mass or more and 24% by mass or less. If the content of the resin (B) is within the range of 3% by mass or more and 40% by mass or less with respect to the total amount of the electromagnetic wave shielding paste, the solvent or dilution is substantially contained in the electromagnetic wave shielding paste as described later.
  • the viscosity that can be filled in the narrow gap or groove can be maintained, and the handleability at the time of manufacturing is improved. Further, the content of the resin (B) having a low volatile rate, which has a volatile rate of 0.1% by mass or more and 20% by mass or less after being held at 130 ° C. for 60 minutes with respect to the total amount of the electromagnetic wave shielding paste, is high. If the amount is within the range of 3% by mass or more and 40% by mass or less with respect to the total amount of the electromagnetic wave shielding paste, voids and resin sink marks (cured product) are contained in the electromagnetic wave shielding paste filled in the narrow gaps or grooves. It is possible to suppress the occurrence of dents on the surface of the paste and form a cured product that exerts a sufficient electromagnetic wave shielding effect.
  • the (C) peroxide acts as a thermal radical polymerization initiator, initiates a polymerization reaction of the resin contained in the electromagnetic wave shielding paste, and cures the electromagnetic wave shielding paste.
  • the peroxide (C) is preferably an organic peroxide having a 10-hour half-life temperature of 40 ° C. or higher and 160 ° C. or lower.
  • the peroxide is an organic peroxide having a half-life temperature of 40 ° C. or higher and 160 ° C. or lower for 10 hours, the resin can be cured at a relatively low temperature, causing heat damage to electronic components.
  • An electromagnetic wave shield can be formed without the need for it.
  • the 10-hour half-life temperature refers to the temperature at which the time required for the amount of peroxide to be decomposed to be halved (1/2) is 10 hours.
  • (C) Peroxide is 2,2-bis (4,5-di-t-butylperoxycyclohexyl) propane (trade name: Pertetra A, manufactured by Nichiyu Co., Ltd., 10-hour half-life temperature: 94.7. ° C.), 1,1-di (t-hexyl peroxy) cyclohexane (trade name: Perhexa HC, manufactured by Nichiyu Co., Ltd .: 87.1 ° C.), 1,1-di (t-butyl peroxy) cyclohexane (trade name: Perhexa HC, manufactured by Nichiyu Co., Ltd.) Product Name: Perhexa C, manufactured by Nichiyu Co., Ltd., 10-hour half-life temperature: 90.7 ° C.), n-Butyl 4,4-di (t-Butyl Peroxy) Valerate (Product Name: Perhexa V, Sun Oil Co., Ltd., 10-hour half-life temperature: 104.5 ° C
  • the content of the peroxide (C) is preferably in the range of 0.1% by mass or more and 1.5% by mass, more preferably 0.2, with respect to 100% by mass of the total amount of the electromagnetic wave shielding paste. It is in the range of mass% or more and 1.2 mass% or less, and more preferably in the range of 0.3 mass% or more and 1.0 mass% or less. If the content of (C) peroxide is within the range of 0.1% by mass or more and 1.5% by mass or less with respect to the total amount of the electromagnetic wave shielding paste, (C) peroxide initiates thermal radicals. By acting as an agent, the radical reaction of the resin (B) proceeds, the electromagnetic wave shielding paste filled in the narrow gap or groove is cured, and a cured product exhibiting a sufficient electromagnetic wave shielding effect can be formed.
  • the electromagnetic wave shielding paste preferably contains substantially no solvent or diluent.
  • substantially free of solvent or diluent means that no solvent or diluent is intentionally added to the electromagnetic wave shielding paste.
  • the solvent or diluent may already be contained in the (A) conductive particles, (B) resin or (C) peroxide contained in the electromagnetic wave shielding paste. Since it is difficult to remove the solvent or diluent contained in (A) conductive particles, (B) resin or (C) peroxide used for the electromagnetic wave shielding paste, (A) conductive particles, The solvent or diluent inevitably contained in the resin (B) or the peroxide (C) may be contained in the electromagnetic wave shielding paste.
  • the electromagnetic wave shielding paste does not substantially contain an organic solvent or diluent means that the solvent or diluent contained in the electromagnetic wave shielding paste is 5 with respect to the total amount of the electromagnetic wave shielding paste. It means that it is less than mass%, and it may be 3% by mass or less, 2% by mass or less, or 1% by mass or less.
  • Organic solvents substantially not contained in the electromagnetic wave shielding paste include methanol, ethanol, propanol, butanol, ethylene glycol, propyl acetate, butyl acetate, dibasic acid ester, ethyl proxitol ethoxypropanol, carbitol acetate, 2 -Methyl-1-methylethyl acetate, carbitol acetate, 2-methoxy-1-methylethyl acetate, dipropylene glycol methyl ether (DNP), ethylene glycol monobutyl ether acetate (BG), methyl isobutyl ketone (MIBK), 2- Butoxyethanol, diethylene glycol monobutyl ether acetate (ECA), 4-methyl-1,3-dioxolan-2-one, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), di
  • the diluent does not contain the resin (B) whose volatilization rate after holding at 130 ° C. for 60 minutes is within the range of 0.1% by mass or more and 20% by mass or less.
  • Examples of the diluent substantially not contained in the electromagnetic wave shielding paste include acrylic resin monomers, oligomers and polymers having a volatilization rate of less than 3% by mass or more than 20% by mass after being held at 130 ° C. for 60 minutes.
  • Specific examples of the diluent in the present specification include acrylate (volatile rate after storage at 130 ° C. for 60 minutes: 100% by mass), butyl acrylate (volatile rate after storage at 130 ° C. for 60 minutes: 100% by mass), and the like.
  • 2-hydroxyethyl acrylate volatile rate after storage at 130 ° C. for 60 minutes: 100% by mass
  • 2-phenoxyethyl acrylate at 130 ° C.
  • Neodencanic acid-2,3-epoxypropyl ester 1,4-butanediol di as a diluent having a functional group other than the (meth) acryloyl group as a diluent substantially not contained in the electromagnetic wave shielding paste.
  • Aminophenyl) -aromatic glycidyl ether selected from methane; epoxyphenol novolac resin containing formaldehyde and glycidyl ether; styrene oxide and ⁇ -pinene oxide; allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate and 1-vinyl-3,4 -A monoepoxide compound with other functional groups selected from epoxycyclohexane; selected from (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether and neopentyl glycol diglycidyl ether. Diepoxide compounds; and triepoxide compounds selected from trimethylolpropane triglycidyl ethers and glycerin triglycidyl ethers; and mixtures thereof.
  • the paste for electromagnetic wave shielding contains (A) conductive particles, (B) resin and (C) peroxide so that each component satisfies the above-mentioned content range.
  • the resin (B) may be blended in the range of 3 parts by mass or more and 67 parts by mass or less with respect to 100 parts by mass of (A) conductive particles, and 5 parts by mass or more and 53 parts by mass or less. It may be blended within the range of 8 parts by mass or more and 43 parts by mass or less, or it may be blended within the range of 10 parts by mass or more and 33 parts by mass or less.
  • (C) peroxide may be blended in the range of 0.1 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of (A) conductive particles, and 0.2 parts by mass. It may be blended within the range of 1.2 parts by mass or more, or may be blended within the range of 0.3 parts by mass or more and 1.0 parts by mass or less.
  • the electromagnetic wave shielding paste can be produced, for example, by blending raw materials composed of (A) conductive particles, (B) resin and (C) peroxide, and stirring and mixing them.
  • the electromagnetic wave shielding paste can be produced by stirring and mixing (A) conductive particles, (B) resin and (C) peroxide using a known device.
  • a known device for example, a Henschel mixer, a roll mill, a three-roll mill, or the like can be used.
  • the conductive particles (A), the resin (B) and the peroxide may be put into the apparatus at the same time and mixed, or a part of them may be put into the apparatus first and mixed, and the rest may be mixed. It may be put into the apparatus later and mixed.
  • Electromagnetic wave shielding paste can be used for electronic components.
  • Examples of electronic components that use the electromagnetic wave shielding paste include power amplifiers, Wi-Fi / Bluetooth modules, and flash memories used in electronic devices such as mobile phones, smartphones, notebook computers, and tablet terminals.
  • the cured product having an electromagnetic wave shielding effect formed by the electromagnetic wave shielding paste has an electromagnetic wave shielding effect of 37 dB or more, preferably 50 dB or more, and more preferably 60 dB or more. By having such a shielding effect, electromagnetic waves can be effectively shielded. This electromagnetic wave shielding effect can be measured in accordance with ASTM D4935.
  • the cured product having an electromagnetic wave shielding effect formed by the electromagnetic wave shielding paste has an adhesion of 5B or more in the evaluation of the cross-cut peel test shown in Examples described later.
  • adhesion for example, a cured product having an electromagnetic wave shielding effect formed on a substrate of an electronic component is less likely to come off.
  • the obtained electromagnetic wave shielding paste can be applied to a substrate or the like and cured to obtain an electronic component having a cured product having an electromagnetic wave shielding effect.
  • the coating method include an inkjet method, a super inkjet method, a screen printing method, a gravure printing method, an offset printing method, a gravure offset printing method, a flexographic printing method, a spray coating method, a dispense coating method, and a jet dispense method.
  • the method for curing the electromagnetic wave shielding paste include heat treatment and ultraviolet irradiation treatment.
  • the jet dispense method When filling a narrow gap or groove formed on a substrate, for example, having a width of 50 ⁇ m or more and 1,000 ⁇ m or less and a depth of 100 ⁇ m or more and 1,000 ⁇ m or less, the jet dispense method is used. It is preferable to use it.
  • the obtained electromagnetic wave shielding paste has a viscosity at 25 ° C. of 10 mPa ⁇ s or more and 200,000 mPa ⁇ s or less as measured by a Brookfield type viscometer at a rotation speed of 50 rpm.
  • the intervals or grooves can also be filled without generating voids or the like during filling.
  • A Conductive particles A1: Flake-shaped 10 ⁇ m silver filler (Product number: FA: SNA-253, DOWA Holdings, Inc., average particle size (major axis average value) 10 ⁇ m)
  • the size of the conductive particles (A) was observed using a scanning electron microscope (SEM), and 50 particles were arbitrarily measured from the SEM image to calculate an average value.
  • SEM scanning electron microscope
  • the average value is used as the average particle size, and when the shape is needle-shaped, elliptical spherical, flake-shaped, or indefinite, the average value on the long axis is used as the average particle size. And said.
  • Resin B1 Polyfunctional polyester acrylate (Product number: CN2279, manufactured by Sartomer)
  • B2 Polyester acrylate oligomer (Product number: CN2281, manufactured by Sartomer)
  • B3 N- (2-Hydroxyethyl) acrylamide (Product name: HEAA, KJ Chemicals Co., Ltd.)
  • B'4 2-Phenoxyacrylate (Sigma-Aldrich Co., Ltd.)
  • B'5 3 Functional Aliphatic Polyester Urethane Acrylate Oligomer (Product No .: CN929, manufactured by Sartomer)
  • C1 Peroxide
  • C2 Bis (4-t-butylcyclohexyl) peroxydicarbonate (trade name: Parloyl TCP, NOF CORPORATION, 10-hour half-life temperature: 40.8 ° C)
  • C3 Cumene hydroperoxide (Product name: Park Mill H, NOF CORPORATION, 10-hour half-life temperature: 157.9 ° C)
  • Examples 1 to 11 Comparative Examples 1 to 4 Each raw material was mixed and dispersed using a three-roll mill so as to have the blending ratio shown in Table 1 below to produce an electromagnetic wave shielding paste.
  • the electromagnetic wave shielding pastes of Examples 1 to 11 are substantially free of solvents or diluents.
  • Viscosity measurement The viscosity of each electromagnetic wave shielding paste in Examples and Comparative Examples is the viscosity (mPa) at 25 ° C. at 50 rpm using a Brookfield type (B type) viscometer (product number: DV-3T, manufactured by Brookfield Co., Ltd.). -S) was measured. (B) The viscosity of the resin was also measured in the same manner. Tables 2 and 3 show the measured viscosities of the electromagnetic wave shielding pastes and the viscosities of the resin (B).
  • Electromagnetic wave shielding effect measurement The electromagnetic wave shielding effect was measured in accordance with ASTM D4935. More specifically, a precision dispenser (product name: Spectrum II dispenser, model number: S2-920P, manufactured by Nordson Asimtech) and a dispense bubble (product name: Dispens Jet, model number: DJ-2200, manufactured by Nordson Asimtech). was attached, and the electromagnetic wave shielding pastes of Examples and Comparative Examples were applied onto a 5 mm square polyimide substrate (thickness 1 mm) and heated at 175 ° C. for 1 hour to cure the electromagnetic wave shielding paste.
  • a precision dispenser product name: Spectrum II dispenser, model number: S2-920P, manufactured by Nordson Asimtech
  • a dispense bubble product name: Dispens Jet, model number: DJ-2200, manufactured by Nordson Asimtech
  • a humidification test (temperature 30 ° C., relative humidity 60%, 168 hours) was performed on each Cu substrate on which the electromagnetic wave shielding paste was cured in a constant temperature bath (product number: THR040FB, manufactured by Advantech Co., Ltd.).
  • a reflow step was performed in the air with a reflow device (product number: TNR15-225LN-M, manufactured by Tamura Corporation) at 260 ° C. and a conveyor speed of 0.25 m / min.
  • cellophane tape manufactured by Nichiban Co., Ltd.
  • Nichiban Co., Ltd. was attached to the intersecting notches, and the attached cellophane tape was quickly peeled off.
  • the area of the coating agent peeled off was measured and evaluated on a scale of 0B to 5B shown in Table 1 below. The results are shown in Tables 2 and 3.
  • the electromagnetic wave shielding effect of the cured product using the electromagnetic wave shielding paste of Examples 1 to 11 was 37 dB or more, which was a good result.
  • the electromagnetic wave shielding pastes of Examples 1, 3, 5, 8, 9 and 11 had an electromagnetic wave shielding effect of 50 dB or more, and exhibited an excellent electromagnetic wave shielding effect.
  • the cured product using the electromagnetic wave shielding paste of Examples 1 to 11 had the best evaluation of 5B among the 6 grades of the cross-cut peel test, and adhered. It was also excellent in sex. From this result, the electromagnetic wave shielding pastes of Examples 1 to 11 have excellent adhesion even when filled in narrow gaps or grooves, and suppress voids and resin sink marks (dents on the surface of the cured product). It was speculated that it would be done.
  • the electromagnetic wave shielding pastes of Comparative Examples 1 to 3 had an electromagnetic wave shielding effect of less than 37 dB, and the electromagnetic wave shielding effect was inferior. Further, the electromagnetic wave shielding pastes of Comparative Examples 1 to 3 had the second lowest evaluation of 1B out of 6 in the cross-cut peel test, and the adhesion was inferior.
  • the electromagnetic wave shielding paste of Comparative Example 4 has a good electromagnetic wave shielding effect of 46 dB and a cross-cut peel test evaluation of 5 B, but has a viscosity of more than 200,000 mPa ⁇ s and dispenses into a narrow gap or groove. It was speculated that it would be difficult.
  • the electromagnetic wave shielding paste according to the first embodiment of the present invention is an electronic component such as a power amplifier, a Wi-Fi / Bluetooth module, and a flash memory used in electronic devices such as mobile phones, smartphones, notebook computers, and tablet terminals. Can be suitably used for.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Conductive Materials (AREA)
PCT/JP2020/037270 2019-10-17 2020-09-30 電磁波シールド用ペースト WO2021075265A1 (ja)

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